Tertiary amine salts of 3, 6-endoxohydro-orthophthalic acids



United States Patent 3,246,015 TERTIARY AMINE SALTS 0F 3,6-ENDOXOHYDRO-ORTHOPHTHALIC ACIDS Harold L. Lindaherry, Aurora, and Walter W.Abramitis,

Downers Grove, 111.; said Lindaherry assignor to Pennsalt ChemicalsCorporation, Philadelphia, Pa., :1 corporation of Pennsylvania, and saidAbramitis assignor to Armour and Company, Chicago, Ill., a corporationof Delaware No Drawing. Original application Nov. 24, 1961, Ser. No.154,887. Divided and this application June 19, 1964, Ser. No. 385,097

Claims. (Cl. 260347.3)

This application is a division of application Serial No. 154,887, filedNovember 24, 1961.

This invention relates to the control of plant life in ponds, lakes, andother bodies of water and deals particularly with the use of certainlong chain amine salts for chemical control of aquatic weeds and algae.

Numerous chemical agents are known to control (i.e. kill or inhibit)aquatic plant growth, but each agent has disadvantages which limit itsusage. For example, there are many potent algicides which cannot be usedbecause at useful concentrations they are extremely toxic to fish. Onthe other hand, some agents may effectively control one species ofaquatic plan-t life and be of little or not value with others. Stillother agents are known which have limited utility because of their highcost (e.g. silver compounds. Thus, there exists the need for improvedmeans to effectively control the many varieties of undesirable weeds,fungi, and algae existing in ponds, lakes, streams, etc.

' It is known that the disod-i-um salt of endothal (6.1g.3,6-endoxohexahydrophthalic acid) can be used for aquatic weed control.This compound is quite effective and is relatively non-toxic to. fish,but it is somewhat slow in its action. It is, of course, desirable thatalgicides act quickly and fast action also aids to avoid loss bychemical degradation as well as dilfusion due to water currents and/ orweather conditions.

It has now been found in accord with this invention that aquatic plantlife can be effectively controlled by use, at low concentrations, ofnovel amine salts of a 3,6-endoxohydro-orthophthalic acid, wherein saidamine salt radical is derived from an amine which is a tertiary alkylamine having the structure N- i R.

where R is an aliphatic hydrocarbon group containing from 12 to 18carbon atoms, and R and R are lower alkyl radicals which may be the sameor different (e.g. methyl, ethyl, propyl, butyl).

The 3,6-endoxohydro-orthophthalic acid salts useful in this inventionwill have less than three double bonds in the endoxocarboxylic acidring, but may have all three degrees of ring saturation and thus willinclude 3,6- endoxodihydro-orthophthalic acids (e.g.)

(If-COO- o-orrrr- 3,6-endoxotetrahydro-orthophtha-lic acids (e.g.)

A J; I \l l/ I o O-COO- 0 0-000- [I 0 I and I 0 II o I o-oo0 -o I 0-000In this group, the later compounds (i.e. the hexahydro compounds)generally have greater activity and are the prefer-red anions to beused.

It will be understood that all of the 3,6-endoxohydropl1- thalic acidsand anhydrides may be used to form salts with the teritia-ry aminesdefined above to give the compounds useful in this invention. Whereanhydrides are used, a mole of water must be used, of course, to causehydrolysis to the dibasic acid. In addition to the unsub stituted acids,monovalen't radical substituted derivatives may be used and suchsubstituents will include halogens (e.g. chlorine, bromine, etc), loweralkyl, lower alkoxy, lower aryl, lower aryloxy, nitro, cyano, haloalkyl(e.g. trifluoromethyl) and like groups. The substituted acids from whichthe salts useful in this invention are derived are described and theirpreparation given in US. 2,576,- 080.

As indicated, the amines from which salts of the above3,6-endoxohydro-orthophthalic acids are derived will be teriti-a-ryalkyl amines. These aliphatic amines may be derived from the well knownaliphatic hydrocarbon amines obtained by reductive arn-in-ation of theacids from animal fats and vegetable oils, particularly tallow andcoconut acids which have predominantly 12 to 18 carbon atoms in thechain. Of particular value for this invention are coconut oil amines(predominantly twelve and fourteen carbon atoms) which have beenconverted to tertiary amines by alkylation. However, other tertiaryamines within the above structural configuration are also operable inthis invention and such amines may be obtained by the amination andsubsequent alkylation of oleic, liuoleic, tallow, and soya acids.Alternatively, these tertiary amines may be obtained by conversion ofthe acids to an amide with a di-lower alkyl secondary amine followed byreduction of the carbonyl group. Specific amines which may be used toform the salts useful in this invention include N,N-dimethyllaurylamine,N,N- diethylmyristyl'amine, N,N-di-propylstearylamine and the like.However, because of availability and cost, mixtures of amines willpreferably be used such as the mixtures found inN,N-di;rnethylc0coamine, N,N-dimethylsoyaamine, etc. The methods ofmaking these amines are well known, the various processes beingdisclosed in the book by Astle entitled Industrial Organic NitrogenCompounds (Reinhold, 1961).

The preparation of the amine salts of the 3,6-endoxohydrophthalic acidsis readily carried out, without need of critical controls, simply bycontacting the desired amine with a stoichiometric amount of the desired3,6-endoxohydrophthalic acid or anhydride. The temperature for thereaction will usually be held between about 30 and C. and the process iscompleted in a short time. It will be understood that both the mono or(ii-tertiary amine salts of the acid or anhydn'de may be prepared andused in this invention. To prepare the mono-salt the stoichiometricamount of amine used will simply be one-half required for the dibasicsalt. The techniques which may be used to prepare these compounds arealso disclosed in US. 2,576,082.

The novel compounds used in this invention when made from'commercialamines are generally clear or slightly turbid tan or brown oils orsyrups which do not readily lend themselves to crystallization. Thisresistance to crystallization is probably due to the fact that thecommercial amines used to form the salts are comprised of more than onediscrete amine species and which a mixture makes crystallizationimpossible. However, this is not important because the amine salt oilobtained as product is simply dissolved in a suitable solvent for use.When individual specific amines are used for salt formation, however,the products are waxy or soap-like solids. The products used in thisinvention are readily soluble in water, ethanol and other alcohols,benzene, toluene, xylene and other aromatic hydrocarbons, diethyl ether,diacetone alcohol, etc. They are, however, insoluble in hexane andsimilar aliphatic hydrocarbon solvents.

The compounds described above act as a contact poison and for thisreason, aquatic weed control is achieved quickly simply by treating thearea with sufficient material to maintain a given strength of activeingredient in the water surrounding the exposed tissue surface area ofthe plant. The activity of the above described compounds is so high thatsatisfactory control is obtained with a concentration of less than onepart per million of active ingredient in solution in the watersurrounding the plants; For most applications where an entire area suchas a pond or lake is treated, concentrations of about 0.05 to 0.5 ppm.will be quite effective with no harm to fish. The preferredconcentration range which is harmless to fish will usually be betweenabout 0.25 to 0.5 ppm. Concentrations as high as .75 ppm. in water hasbeen observed to be safe to fish under field conditions. For resistantweeds where no fish are present a dosage'of up to about 3 ppm. may beemployed.

The manner in which the water area may be treated will vary with thespecific problems encountered. Since the active ingredient is watersoluble it will diffuse out from the area treated. However, in thisinvention this is not serious because of the very fast action of theagents. -In treating small areas where the Weed problem is usuallycritical around the edge of the pond it is more practical to treat themarginal area from the bank than to treat from the center. Furthermore,because of the diffusion of the agents toward the center in staticwater, control will be obtained there also. Although aqueous solutionsare usually preferred for economic reasons, solutions of the amine saltsin other solvents may be used and such solutions used for the watertreatment.

Treatment is accomplished best by spraying on the water or by injectionjust below the water surface with distribution as evenly as possible inthe area to be treated. Spraying equipment is preferably used withaqueous solutions and because the agent is applied as an aqueoussolution no problem of preparation, operation or cleaning is involved.In general, the diluted treating solution will contain about to about25% by weight of active ingredient. Although the product is watersoluble at the concentrations used, it may frequently be desirable toincorporate a small amount of a dispersant as a mixing aid in theinitial concentrate used to prepare the diluted treating solutions. Forthis purpose isopropyl alcohol, diacetone alcohol or other water solublealcohols or ketones may be used. Where a dispersant is used theformulated concentrate will usually contain from about to 30% of thedispersing agent. In order to aid in the estimation of the gallonage ofa active aque- 4 ous solution for various pond sizes the following tableis given:

TABLE I.-APPROXIMATE GALLONS OF 20% ACTIVE AGENT CONCENTRATE NEEDED TOTREAT ONE ACRE 5 OF POND SURFACE (APPROX. 208 BY 208) As is evident fromthe table the concentrations and depths are directly proportional andother concentrations and depth requirements may be calculatedaccordingly In addition to treating the area with a solution by aspraying technique the treating agents may also be formulated in agranular form and applied by any of the variety of manual, electricaland gas-powered whirling spreader-s on the market and which can beadapted for use on boats. This granular formulation consists of anapproximately 1% to 10% (preferably about 5%) concentration of activeagent deposited on any inert material such as Attapulgite, Bentonite andother inert adsorbent granulated clays having a size range of about 8 to30 mesh (U.S. sieve size).

The granular formulations can be simply prepared by spraying the liquidactive ingredient or concentrates thereof into the granular inertcarrier in a rotating or other suitable blender common to the trade forpreparation of pesticide formulations. Although the granulatedformulations can be prepared containing from 1 to 25% of activeingredient it has been found that 5% of the active ingredient isgenerally the best concentration to use for obtaining good distributionwhen the formulation is applied To treat one acre of water surface witha 5% by weight granular formulation at a level of one part p er millionof active agent will require 55 pounds of the granular material for eachfoot of pond depth. Since again the depth of pond and the doseconcentration are directly proportional, the amount of granularninterial for other depths and at other concentrations may be readilycalculated. Use of a granular formulation is advantageous for control ofsubmerged algae since the granular agent sinks to the bottom of thepond.

As indicated, the active agents described above are effective in accordwith this invention for the control of plant life in aquatic systems.One of the particular advantages of the invention is that it enables awide variety of plant life to be controlled with a single activeingredient, i.e. the agents have .broad spectrum activity. The salts asdescribed above are effective against practically all aquatic plants andgrowth which cause problems on lakes, ponds, rivers, streams, etc. Thusthe invention is useful in controlling pondweeds (Potamogeton spp.),including bassweed, curly leaf pondweed, floating-leaf pondweed, sagopondweed, flat-stem pondweed, bushy pondweed (Naias spp.), hornedpondweed (Zanichellia sp.) coontail (Ceratophyllum sp.), water milfoil(Myriophyllum spp.), mud plantain and water stargrass (Heterantheraspp.), bladderwort (Utricularia spp.), burr weed (Sparganium spp.),tapegrass, Wild celery, belgrass 70 (Vallisneria sp.), waterweed (Elodeaspp.), members of the duckweed family, such as big duckweed (Spirodellasp.), duckweed (Lemna spp.), watermeal (Wolffia spp.), stonewort,muskgrass (Chara spp.) and the filamentous green algae known as pondscum (Cladophora, Spirogyra, Pithophora, Rhizoclonium, Ulothrix). Inaddition, the

invention is useful for the control of slime causing bacteria, such asAerobacle r aerogenes, Bacillus micoide's, Pseidomonas originosa. Alsoof interest is the use of the above materials to control thesub-tropical marine algae Gyi nllOdilll lllTl brevz's, which causes thered tide disease in fish.

In addition to use in ponds and lakes, this invention is applicable tothe control of algae and slime forming bacteria in cooling towers andother water recirculating systems as used in paper manufacturingprocesses for example, in drainage ditches and other water flowingsites.

In order to more fully describe and illustrate the invention, thefollowing examples are given:

EXAMPLES All parts given are parts by weight EXAMPLE 1 A reaction vesselwas charged in order with 559 parts (2.62 moles) ofN,N-dimethylcocoamine (chain length distribution: 49% c 12, 17% 14, 9%C-16, 10% C-18, balance C and C 62 parts of water, 69 parts (2.16 moles)of methanol, and 190 parts (1.14 moles) of 3,6endoxo-A-4-tetrahydro-orthophthalic anhydride. As stirring occurred aslight temperature rise to about 35 C. was noted. The product at thispoint was the amine salt of the acid obtained from the hydrolysis of theanhydride. Then 3 parts of Raney nickel and parts of methanol were addedand hydrogen pressured in at 150 p.s.i.g. for two hours to reduce thedouble bond and thus convert the tetrahydro-orthophthalic acid moiety toa hexahydrophthalic acid. The temperature during the hydrogenation roseto 38 C. After cooling, the product obtained was an 83% aqueous methanolsolution of dimethyl cocoamine salt of 3,6-endoxohexahydro-orthophthalicacid.

The above product was diluted with water to a concentration of 21% andwas ready for use. Additionally, a 72% solution of the salt in diacetonealcohol was prepared which is diluted with water to 20% for use in thefield.

The compound of Example 1 before reduction and the dimethylcocoaminesalt of 3,6-endoxohexahydrophthalic acid were evaluated againstChlorella (Wisconsin strain). The data obtained together with acomparison of the effectiveness of a conventional quaternary ammoniumalgicide are shown in Table II.

TABLE IICIILORELLA TOXICITY TESTS Organism-Chlorella (Wisconsin Strain)Initial coneentration-300,000 cells/ml.

48-hour concentration (Control)3,250,000 cells/nil. Medium-Allens pHrill/50 ml. Erlenmeyer) EXAMPLE 2 The di-dimethylcocoamine salt of3,6-endoxohexahydro-orthophthalic acid was evaluated as an algicide atDRO-O RTHOPHTHALIO ACID A GA I N S T VA R I O U S AQUATIC ORGANISMSAquatic organism Observations on effective concentration Poudweeds:

Potamogeton deversi folius Effects noticed at 0.01 P. foliosus p.p.rn.Control P. nodosua. obtained at 0.05-0.10 Najas flem'lis p.p.m.

Filamentous algae: vartialbze {GSpOIjlSG obtained a o 0.0 p.p.rn. glgfgggfg Complete toxicity ob- S in) p m tained at 0.1 to 0.5 p.p.m. p gy t%v)en in cold water (55 Muskgrass (Chara uulgaris) Temporary controlWater-weed (Elodea canmlmsis) achieved at 0.1 p.p.rn. False loosestrife(Ludwigiu palustn's) Emergent species:

Jussiaea (Water primrose) Spray application at 0.5 Duekweed (Lemnaminor). to 1.0 p.p.rn. gave Sweetfiag (Acorns calamus) otiectivecontrol.

EXAMPLE 3 Following the details of Example 1, but using one-half theamount of N,N-dimetylcocoamine, the mono-dimethylcocoamine salt of3,6endoxohexahydro-orthophthalic acid was prepared. This compound inaqueous solution at 0.4 p.p.rn. killed the subtropical marine algae(Gyrodinium brevis) which causes the red tide disease of fish.

EXAMPLE 4 The slirne causing bacteria Aerobacter aerogenes and Bacillusmycoides were completely killed in laboratory culture tests at 0.5 and 1ppm. respectively of the compound of Example 1.

EXAMPLE 5 Instead of using N,N-dimethylcocoamine in Example 1, atallowamine (26% C16 and 72% C-18) is alkylated with a tertiary aminemixture. Two moles of this product reacted with one mole of3,6-endoxodihydro orthophthalic acid yields the salt, which is found toinhibit growth of Elodea canadensis, Pot omogeton pectinatus, andPotomogeton crispus at 0.16 and 0.32 ppm.

EXAMPLE 6 The effect of the dimethyl cocoamine salt of3,6-endoxohydro-orthophthalic acid (the product of Example 1) onsubmersed weeds was evaluated and compared with the disodium salt of3,6-endoxohexahydro-orthophthalic acid (Endothal). In order to obtaincomparative results in a short time, high concentrations of agent wereused in the test. Tablev 4 indicates the test concentrations andresults: I

TABLE IV.TIME VS. CONCENTRATION EVALUATIONS WITH SUBMERSED WEEDS [Najasguadalupensis-southem naiad. Averages of 3 replicate tests It is clearfrom the above table that the tertiary amine salt of this invention ismuch faster acting than Endothal. This permits aquatic weed controleither in a shorter time at a given concentration or a lowerconcentration of active agent for control in a given time.

EXAMPLE 7 To 2.4 g. (0.01 mole) of4,5-dich1oro-3,6-endoxohexahydro-orthophthalic anhydride there was added4.3 g. (0.02 mole) of dimethylcocoamine and the components thoroughlymixed. Then, with stirring being continued 0.18 g. (0.01 mole) of waterwas added and a temperature rise from room temperature to 40 to 50 C.was noted. The clear, tan colored syrup obtained was the desiredproduct: di-dirnethylcocoamine salt of 4,5-dichloro-3,6-endoxohexahydrophthalic acid which was soluble in water, diethylether, benzene and diacetone alcohol, but insoluble in hexane. I

The above product was evaluated against coontail (Ceratophyllum sp.) andwas found to give 100% control at 0.5 parts per million.

EXAMPLE 8 Instead of using the N,N-dimethylcocoamine salt in EX- ample2, the N,N'-dimethylsoyaamine salt may be used with equal effectiveness.

Likewise the N,N'-dimethylstearyl amine salt may be used withessentially the same results.

EXAMPLE 9 The following non-aqueous formulations using thedidimethylcocoamine salt of 3,6-endoxohexahydro-orthophthalic acid asactive agent were prepared and successfullyv used against aquatic weeds:

Percent by Sp. gr. of

weight solution Active agent 72. 4 950 Diacetone alcohol 27.6

Active agentv 36. 2 Heavy aromatic naphtha 33. 2 901 Xylene 30. 6

Active agent 55.0 Diacetone alcohol 17. 935 Heavy aromatic naphtha 27. 5

Active agent 49. 4 Heavy aromatic naphtha 14. 5 897 Xylene 30. 4 Butylalcohol 5. 6

Active agent 49. 5 Heavy aromatic naphtha 16. 7 900 Xylene 34.0

The novel compounds of this invention also have utility as soilfungicides. This is demonstrated by the following example:

EXAMPLE 10 The di-dimethylcocoamine salt of3,6-endoxohexahydro-orthophthalic acid was applied to soil at aconcentration of 10 parts per million and the soil so treatedshowedactivity against Phytophthora cactorum, P. cinnamoni, and P.citrophthora. Seedlings planted in the treated soil showed betteremergence than seedlings planted in untreated soil, thus furtherillustrating the effective soil antifungal activity of the compound.

EXAMPLE 11- Following the general details of Example 1 the N,N-dimethylcocoamine salt of 3,6 endoxodihydro-orthophthalic acid isprepared, the 3,6-endoxodihydro-orthophthalic acid being obtained by thecondensation of acetylenedicarboxylic acid and furan in the usualDiels-Alder type condensation. This salt also shows activity againstaquatic Weeds.

It will be understood that the above description and examples are not tobe considered as limiting the invention and that numerous departures maybe made from the above without departing from the spirit and scope ofthe invention.

We claim:

1. A tertiary amine salt of a 3,6-end0Xohydro-orthophthalic acidselected from the group consisting of unsubstituted and substituteddihydro-, tetrahydro-, and heXahydro-orthophthalic acids wherein thesubstituent of said substituted acids are selected from the groupconsisting of halogen, lower alkyl, lower alkoxy, phenyl, phenyloxy,nitro, cyano, and triiluoromethyl wherein said amine portion of saidsalt is a cation of an amine of structure N Rl R3 wherein R is asaturated aliphatic hydrocarbon group containing from 12 to 18 carbonatoms and R and R are lower alkyl radicals.

2. A tertiary amine salt as defined in claim 1 wherein the orthophthalicacid is 3,6 endoxohexahydro-orthophthalic acid.

3. A tertiary amine salt as defined in claim 1 wherein the orthophthalicacid is a dichloro 3,6-endoxohexahydroorthophthalic acid.

4. A tertiary amine salt as defined in claim 1 wherein the orthophthalicacid is 3,6-endoxotetrahydro-orthophthalic acid.

5. The monodimethylcocoamine salt of 3,6-endoxohexahydro-orthophthalicacid. 7 t

6. The monodimethylcocoaminesalt of 3,6-endoxo-A-4-tetrahydro-orthophthalic acid.

7. The monodimethylcocoamine salt of 4,5-dichloro-3,6-endoxohexahydro-orthophthalic acid.

8. The di-dimethylcocoamine salt of 3,6-endoxohexahydro-orthophthalicacid. y

9. The di-dimethylcocoamine salt of 3,6-endoxo-A-4-tetrahydro-orthophthalic acid.

10. The di-dimethylcocoamine salt of 4,5-dichloro-3,6-endoxohexahydro-orthophthalic acid.

References Cited by the Examiner UNITED STATES PATENTS 2,576,080 11/1951Tischler et a1. 260-347.3 2,576,083 11/1951 Tischler 260-3473 NICHOLASS. RIZZO, Primary Examiner.

1. A TERTIARY AMINE SALT OF A 3,6-ENDOXOHYDRO-ORTHOPHTHALIC ACIDSELECTED FROM THE GROUP CONSISTING OF UNSUBSTITUTED AND SUBSTITUTEDDIHYDRO-, TETRAHYDRO-, AND HEXAHYDRO-ORTHOPHTHALIC ACIDS WHEREIN THESUBSTITUENT OF SAID SUBSTITUTED ACIDS ARE SELECTED FROM THE GROUPCONSISTING OF THE HALOGEN, LOWER ALKYL, LOWER ALKOXY, PHENYL, PHENYLOXY,NITRO, CYANO, AND TRIFLUOROMETHYL WHEREIN SAID AMINE PORTION OF SAIDSALT IS A CATION OF AN AMINE OF STRUCTURE